A tandem synthesis of 3-aroylcoumarinoflavones catalyzed by <Emphasis Type="SmallCaps">l</Emphasis>-proline and their antioxidant activity

A facile, convenient, efficient and high-yielding synthesis of 3-aroylcoumarinoflavones has been developed by the condensation of easily synthesized 7-hydroxy-8-formylflavones and benzoyl acetonitriles in the presence of catalytic amount of l-proline in ethanol reflux. All the synthesized compounds were evaluated for their antioxidant activity. Some of the compounds showed very good activity compared to standard BHT.     

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (T_NTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of T_NTBN was estimated for CBO3OCB and T_NTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of T_NTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.     

Solid-State 13C NMR Evidence for Long Multicenter Intradimer Bonding in Zwitterion-like Structures

The principal values of the ¹³C chemical shift tensor for the β and δ polymorphs of π-[TTF⋅⋅⋅TCNE] (TTF=tetrathiafulvalene; TCNE=tetracyanoethylene) have been analyzed to understand the abnormally long intra-dimer bonding of singlet π-[TTF^δ+⋅⋅⋅TCNE^δ−]. These structures possess 12 intradimer contacts <3.40 Å, with the shortest intra π-[TTF⋅⋅⋅TCNE] separations involving 2-center (2c) C−S and 3c C−C−C orbital overlap contributions between the [TTF]^δ+ and [TCNE]^δ−. This solid-state NMR study compares the [TTF⋅⋅⋅TCNE] ¹³C tensor data against previously reported π-[TTF]₂²⁺ and π-[TCNE]₂²⁻ homo-dimers to determine how the tensor principal values change as a function of electronic structure for both TTF and TCNE moieties. In the β and δ phases of [TTF⋅⋅⋅TCNE], the TCNE ethylenic ¹³C shift tensors predict TCNE oxidation states of −0.46 and −0.73, respectively. The TTF sites are less similar to benchmark ¹³C data with the β-phase differing primarily in the ethylenic π-electrons. The δ form differs significantly from the homo-dimer data at all principal values at both the ethylenic and CH sites, indicating changes to both the π-electrons and σ-bonds. In both hetero-dimer phases, the NMR changes supports long bond formation at nitrile and CH sites not observed in homo-dimers.     

Synthesis and self‐assembly of diblock copolymers composed of poly(3‐hexylthiophene) and poly(fluorooctyl methacrylate) segments

Regioregular poly(3‐hexylthiophene)‐b‐poly(1H,1H‐dihydro perfluorooctyl methacrylate) (P3HT‐b‐PFOMA) diblock copolymers were synthesized by atom transfer radical polymerization of fluorooctyl methacrylate using bromoester terminated poly(3‐hexylthiophene) macroinitiators in order to investigate their morphological properties. The P3HT macroinitiator was previously prepared by chemical modification of hydroxy terminated P3HT. The block copolymers were well characterized by ¹H NMR spectroscopy and gel permeation chromatography. Transmission electron microscopy was used to investigate the nanostructured morphology of the diblock copolymers. The block copolymers are able to undergo microphase separation and self‐assemble into well‐defined and organized nanofibrillar‐like micellar morphology. The development of the morphology of P3HT‐b‐PFOMA block copolymers was investigated after annealing in solvent vapor and also in supercritical CO₂. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Harmful Substances on the Opera Stage: Possible Negative Effects on Singers'' Respiratory Tracts

Objective, quantitative information is lacking in the medical community about actual working conditions for professional singers onstage, and moreover, about which conditions are safe. Physicians, speech-language pathologists, and speech scientists focusing on laryngology should have relevant information about the opera as workplace and the medical sequelae of unhealthy environments. We describe five toxic substances to which singers presenting to our clinics were exposed while working professionally on the opera stage: (1) aromatic diisocyanates, (2) penicillium frequentans in cork granulate, (3) formaldehyde in cork granulate, (4) cobalt and aluminum (pigment components), and (5) quartz sand capable of entering the alveolae. Biological considerations and clinical data for some subjects suggest a direct causal link between the exposures and the patients' complaints and findings. Our observations suggest that whenever singers complain about deleterious conditions such as dry and hot onstage climate or suspicion of the presence of harmful substances, the specific conditions existing in the theater in question should be investigated. Harmful substances are not only poorly tolerated by singers, but also they should be preventable.     

Laryngeal and Vocal Changes During Vagus Nerve Stimulation in Epileptic Patients

Left vagus nerve stimulation (VNS) by means of an implanted electrode has proven to reduce seizure frequency in epileptic patients with medically refractory seizures. This technique is now widely applied over the world. Voice changes appear to be one of the major side effects. The morphodynamic changes in the larynx and the acoustic impacts have been analyzed in detail in 7 implanted patients. Basic vagus stimulation is well tolerated. Extra stimulation induces an adductory spasm of either the ipsilateral vocal fold or the vestibular fold. The result, when the patient phonates, consists of a slight increase of F0 as well as a moderate increase of random period perturbation, but there is no evidence for the occurrence of "bifurcations." Further, as the glottic closure remains sufficient, there is no increase in turbulent noise. The lack of increase in turbulent noise and the lack of "bifurcations" appears to clearly differentiate a spasmodic contraction of the vocal cord from a unilateral vocal fold paralysis.     

Bilateral Vocal Fold Posterior Glottic/Subglottic Stenotic Web Resected with Contact Tip Nd-YAG Laser

The standard treatment for respiratory failure remains endotracheal intubation, with periods of 22 or more days being commonplace. Posterior glottic stenotic web formation, from scarring in the posterior interarytenoid area, may occur after endotracheal intubation, thermal, corrosive, or direct surgical injury. A commonly used classification system for posterior glottic stenosis divides the occurrence into four types. Type I involves an interarytenoid scar band between the vocal folds that is anterior and separate from the posterior interarytenoid mucosa. Type II stenosis involves scarring of the mucosa or musculature of the posterior interarytenoid area. Types III and IV involve unilateral and bilateral cricoarytenoid joint fixation, respectively. Strobovideolaryngoscopy (SVL), rigid and flexible fiberoptic bronchoscopy, electromyography (EMG), radiologic imaging of the neck, larynx, and trachea as well as pulmonary function tests, including flow volume loops, provide important objective measurements of upper airway obstruction. A representative case of a professional voice user who suffered a Type II posterior glottic stenosis is presented. The treatment utilized a specific contact-tip neodymium-yttrium aluminum garnet (Nd-YAG) laser delivery system to achieve precise cutting, vaporization, and coagulation simultaneously, returning tactile touch technique to the airway/voice surgeon. Completely successful restoration of voice and airway have been maintained for 2 1/2 years postoperatively.     

Botulinum Toxin Type B for Treatment of Spasmodic Dysphonia: A Case Report

Although treatment with botulinum toxin type A (BTXA) has become the standard of care for most patients with laryngeal dystonia, its use is limited by the development of resistance to the toxin in some patients. Botulinum toxin type B (BTXB) has been found to be safe and effective in the treatment of cervical dystonia, but it has not been used previously to treat spasmodic dysphonia. Our experience with BTXB in a patient who developed resistance to BTXA suggests that BTXB may be safe and effective for the treatment of laryngeal dystonia, as well.     

Bilateral Mixed Laryngoceles: Simultaneous Strobovideolaryngoscopy and External Video Examination

A music medicine practice affords a unique opportunity to diagnose and treat laryngeal music performers. Strobovideolaryngoscopic (SVL) and external video examination of the voice professional or brass instrument player may focus on the vocal folds, yet abnormalities of the supraglottis, neck, and thorax should be appreciated and documented. Laryngoceles are uncommon laryngeal disorders but may occur in up to 5% of benign laryngeal lesions. While many laryngoceles are asymptomatic, they may cause a cough, hoarseness, stridor, sore throat, pain, snoring, or globus sensation. In particular, musicians who play brass instruments are at high risk for laryngocele development. We highlight two patients with symptomatic laryngoceles to present anatomical, historical, classification, epidemiological, diagnostic, and management considerations.     

APPLICATION OF SHELLAC IN POLYMERS

Abstract

Lac is the only known natural resin of animal origin. It is the secretion of a tiny insect known as Kerriar lacca (formally called Laceifer lacca). The lac-forming tiny insect grows on some types of trees, mostly abundant in tropical countries, including India. The secretion of the lac insect hardens in air and forms a covering on the body of the insect. This covering or the nest forms a continuous incrustation on the branches of the host trees. Lac is collected by scraping the incrustation from the branches of the trees.